Sheet material

ABSTRACT

A sheet material having leather-like grain, excellent scuffing and abrasion resistance and superior dyeability comprising in combination, a substrate, an intermediate layer of 0.05 to 2.5 mm thickness consisting of a finely napped porous polymer bonded to said substrate and an upper layer consisting of a polymeric coating of thickness ranging from 1-100 microns. In typical embodiments, the upper layer may be a polymeric coating material such as linear or cross-linked polyurethanes, the intermediate layer may be a porous polyester, polyamide, vinyl or elastomeric polymer, e.g. a polyurethane, and the substrate may be a woven or non-woven fabric. The upper layer is a laminar structure comprising a plurality of laminae, the bottom lamina consisting of a cross-linked polyurethane elastomer.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of application Ser. No. 64,721, filed on Aug. 18, 1970 now abandoned.

This invention relates to a novel sheet material. More particularly, it relates to a sheet material which is superior in appearance and surface properties.

Substrates, such as cloth, coated by a polymer paste and substrates bonded to a porous polymeric layer have been conventionally used as sheet materials. However, the former sheet materials are rigid, heavy and cold to the touch, though excellent in surface scuffing resistance and abrasion resistance because of direct polymer coatings. The latter is inferior in surface scuffing resistance, abrasion resistance and in dyeability because of the porous polymeric structure, though it can be made flexible, light and soft to the touch by adjusting the porosity properties of the polymer.

It is an object of the present invention to provide a sheet material having good leather-like grain, excellent surface scuffing and abrasion resistance and superior dyeability. Other objects will be apparent from the following description of this invention.

The foregoing objects have been accomplished in a simple and effective matter by the novel sheet material of this invention.

The invention will be described in conjunction with the drawing in which FIGS. 1 and 2 are sectional views of the sheet material of this invention.

Referring to FIGS. 1 and 2 the sheet material of this invention comprises a substrate 1, an intermediate layer 3 and an upper layer 4, said layer 3 consisting of a finely napped porous polymeric layer adhering to the substrate 1 and the upper layer 4. In FIG. 1 the naps 2 are in a substantially upright position. In FIG. 2, which represents a preferred embodiment, the naps 2 of the finely napped porous polymeric layer are laid down. The upper layer 4, consists of a non-porous laminar polymeric coating of thickness ranging from 1 to 100 microns, preferably 5 to 30 microns, as is shown in the drawing. This upper layer comprises a plurality, preferably 2 or 3, laminae, the bottom lamina consisting of a cross-linked polyurethane elastomer.

In the sheet material, according to the present invention, the non-porous polymeric coating of 1 to 100 microns thickness provides high scuffing and abrasion resistance and dyeability, and the finely napped porous polymeric layer below it provides the feeling of softness. Further, a balanced combination of said external polymeric coating and the internal finely napped layer provides a good calf leather-like grain appearance which cannot be obtained with conventional sheet materials, thus remarkably enhancing its commercial value as a substitute product for leathers used for shoes, bags, furniture coverings and the like.

The finely napped porous polymeric layer is obtained by abrading or tearing a porous polymeric layer formed by the coagulation of a polymeric solution layer or the foaming of a polymeric layer or solution layer or by bonding polymeric particles having a porous structure to each other. The porous polymeric layer may be bonded to the substrate after the layer has been formed or alternatively, the porous polymeric layer may be formed directly on the substrate. The state of napping can be controlled by the manner of abrading and tearing the conditions of coagulation and foaming. It is most preferable to use a napped layer obtained by abrading or tearing a macro-porous polymeric layer obtained by wet-coagulating a polymeric solution layer in a coagulation bath containing non-solvent for the polymer.

The finely napped porous polymeric layer is characterized by a thickness of approximately 0.05 to 2.5 mm, preferably 0.1 to 1.0 mm and a density of approximately 0.10 to 0.30 g/cc and a nap length in the range of approximately 0.03 to 0.5 mm. The naps may be randomly bar, plate, polygon and pyramidal in shape and they may have other complex shapes. The napped layer comprises minute pores of approximately 0.1 to 100μ in diameter. The porous substrate is preferably positioned beneath the napped layer so as to strengthen the naps.

Among the polymers which may be used for the construction of the porous polymeric layer are the following: condensation polymers such as polyesters, e.g., polyethylene terephthalate and polyamides, e.g., nylon-6 and nylon-6,6; vinyl polymers and vinyl copolymers such as polyacrylonitrile, polyvinylacetate, polyvinyl alcohol, polypropylene, polyvinyl chloride, polyethylene, vinyl acetate-acrylonitrile copolymers, polymethacrylic acid esters, polyacrylic acid esters, and the like; elastomeric polymers such as linear polyurethane elastomers (PUE), cross-linkable binary liquid polyurethane elastomer (PUE), polyisoprenes, acrylonitrile-butadiene copolymers, styrene-butadiene copolymers and the like.

Polyurethane elastomers and mixtures of the polyurethane elastomers and other polymers described above are preferably utilized because of their desirable elastic and physical properties.

The porous polymeric layer is pressed and condensed by approximately 10 to 90%, preferably 40 to 70%, from the original thickness by means of heated rolls, heated plates and the like, thus obtaining a layer having a density of approximately 0.20 to 0.50 g/cc. In order to produce, with ease, sheet material having a good appearance and excellent surface properties, it is preferable that said layer, prior to compression by application of heat and pressure with a heated plate or rolls, be treated with a swelling agent for the polymer, or a solution of a polymer dissolved in the swelling agent, or preferably a two-liquid type curable polyurethane elastomer comprising a basic material and a cross linker. After the surface is made flat, the porous polymeric layer contains minute voids of approximately 0.1 to 50 microns in diameter and voids of approximately 20 to 500 microns due to laying down the naps.

If an ordinary porous polymeric layer is pressed and heated to make a flat surface, the porous structure will be destroyed and thus the formed surface will be as rigid and poor in vapor permeability as prior sheet materials directly coated with polymers. On the contrary, the present invention provides sheet materials of flexible and soft texture and excellent vapor permeability because the porous structure of the polymer remains substantially intact even after surface treatment, and intervening spaces exist in and between the compressed interlocking naps.

Surface scuffing resistance and abrasion resistance of the final product of the invention are enhanced when the naps of the porous polymeric layer are bound one to another after surface treatment by application of a polymeric solution of a cross-linking two-liquid type polyurethane to the napped porous polymeric layer during the step of laying down the naps. As the polymeric material to be applied to the finely napped, porous polymeric layer, there may be used the polymer used to make the porous polymeric layer, preferably a substantially linear PUE which is soluble in a solvent and is of the cross-linkable two-liquid type PUE. It is preferable to use a solvent which does not substantially liquify the polymeric material composing the naps, though any solvent is applicable if the polymer used is soluble therein. It is most preferable to use a volatile solvent.

The two-liquid type PUE to be used in making the napped porous polymeric layer, comprises (1) the basic material which is a high molecular polyhydroxyl compound having reactive hydroxyl groups at its both ends and which may be prepared by reacting relatively low molecular weight polyhydroxyl compound with polyisocyanate to obtain a higher molecular weight polymer, and (2) the cross-linker which is a high molecular polyisocyanate compound which has at least two reactive isocyanate groups.

As polyhydroxyl compounds to be used as the basic material, there may be named poly-polyalkylene-ether glycols with a molecular weight of 500 to 5,000 such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polyols of low molecular weight such as ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol and hexanetriol and polyester glycols with molecular weights of 500 to 5,000 such as polyethylene adipate, polybutylene adipate and polycaprolactone glycol.

As isocyanate compounds to be used as the crosslinker, there may be named compounds with aliphatic and/or aromatic diisocyanate groups such as toluene diisocyanate, naphthylene diisocyanate, p,p'-diphenylmethane diisocyanate (abbreviated to MDI hereinafter), xylylene diisocyanate, hexamethylene diisocyanate and the like.

As solvent for the basic material and cross-linker there may be used any solvent which dissolves them. It is, however, preferred to use a solvent which does not liquify a major part of the porous structure if the solution is to be applied to the naps. The porous structure may be swollen unless most part thereof is dissolved. It is possible to add a solution of a catalyst to accelerate reaction, dyestuffs, pigments and various stabilizers to the above basic material and cross linker for the two-liquid type polyurethane.

The polymeric solution of the two-liquid type polyurethane is applied to the porous polymeric layer by ordinary means such as by spraying, brushing, knife coating, coating by extruding a coating substance through a slit, roll coating by flat roll or gravure roll and dipping. The type and quantity of solid components in the solution are selected to fit the uses of the product. It is preferred that the surface of the finely napped porous polymeric layer be made flat under high pressure and elevated temperature after most of the solvent of the applied polymer solution or two-liquid type polyurethane has been evaporated and before the cure of the two-liquid type polyurethane has been completed, that is, after a period in the range of 1 minute to 24 hours has passed, depending upon the conditions of temperature and air velocity. The two-liquid type polyurethane is apt to adhere to the surfaces used for applying compression to the layer if it stands for a shorter time than the above-stated period, whereas it is apt to provide insufficient pressing effects if left to stand too much longer than the above-stated period before compression is applied. The temperature depends on the kinds of polymers comprising the napped layer, the optimum temperature for the afore-mentioned polymers ranging between 30° C and 200° C. There may be used rolls and plates with surface, which may be smooth or embossed with a leather-like pattern, to lay down the naps of the napped layer. The thickness of the napped layer is decreased by approximately 10 to 90% under pressure of the above treatment and consequently the final thickness thereof is decreased to approximately 10 to 90% of the original thickness. The napped layer is provided with sufficient vapor permeability, but with insufficient scuffing resistance if there is a too small decrease of thickness, whereas it is provided with excellent scuff resistance but with reduced vapor permeability in the case of a too large decrease of thickness. It is concluded from the foregoing that the required range of decrease in thickness lies between 10 and 90%, preferably from 40 to 70%, of the original thickness.

After the surface treatment, the solvent is removed, if necessary. When the two-liquid type polyurethane is used, it is left to complete curing thereof.

As the polymeric material to be used as the upper layer, it is preferred to use the polymeric material used to make the porous polymeric layer. It is preferred to use a linear solvent-soluble polyurethane elastomer, a cross-linked polyurethane elastomer or a blend of a polyurethane elastomer and other polymer of the above-mentioned classes in order to obtain a product with high abrasion resistance, soft feel and excellent dyeability. The polymeric material may contain dyestuffs, pigment, stabilizer and antistatic agent.

Each successive lamina of the upper layer may be applied by roll coating or spraying a polymeric solution or dispersion or by the process by which the previously formed polymeric layer was bound to the napped surface by means of an adhesive or by heating action or by making use of an adhesive to adhere a preformed self-supporting film of polymer. It is preferable to transfer and bond the lowest lamina of the polymeric coating formed on a support to the napped surface by means of an adhesive or by heating action or under conditions such that slight fluidity still remains after the polymeric solution is spread over the support and most of the solvent of the solution is removed by evaporation. The method in which the polymeric solution is not directly applied to the napped surface is superior because the napped surface is not damaged even with use of a solution of a polymer in which the solvent can dissolve the polymeric substance forming the napped, porous layer, and further, the polymeric layer to be bonded is held by the support until it is transferred, so that it is not necessary to handle it by itself in an unsupported state.

As the support, there may be used a sheet, plate or roll made of metal or synthetic resin, such as polyethylene, polypropylene, polyvinyl alcohol, polyamide, polyester, polytetrafluoroethylene, polytrifluroethylene, silicone rubber. Release paper covered with a synthetic resin mentioned above, may also be used. In order to obtain leather-like surface pattern, it is possible to emboss upon the sheet, plate or roll a leather-like pattern.

The upper layer comprises a plurality of laminae, preferably 2 or 3 laminae, the lowest of which -- i.e. the lamina applied to the napped porous polymeric layer -- is a cross-linked polyurethane elastomer. Examples of desirable upper layers are shown in the following Table I.

                                      TABLE I                                      __________________________________________________________________________     Upper Layer                                                                       Top Lamina       Middle Lamina    Lower Lamina                              Case                                                                              (Composition and Thickness)                                                                     (Composition and Thickness)                                                                     (Composition and Thickness)               __________________________________________________________________________     1  A cross-linked PUE of 0.2-20μ,                                                               A solvent-soluble substantially                                                                 A cross-linked PUE of 0.4-                   preferably 1-6μ thick.                                                                       linear PUE of 0.4-40μ, pre-                                                                  40μ, preferably 2-12μ                                   ferably 2-12μ thick.                                                                         thick.                                    2  A solvent-soluble substan-        A cross-linked PUE of 0.6-                   tially linear PUE of 0.4-40μ,                                                                None             60μ, preferably 3-20μ                  preferably 2-10μ thick.        thick.                                    3  A solvent-soluble substan-                                                                      A solvent-soluble substantially                                                                 A cross-linked PUE of 0.4-                   tially linear polymeric                                                                         linear PUE of 0.4-40μ, pre-                                                                  40μ, preferably 2-12μ                  material of 0.2-20μ, pre-                                                                    ferably 2-12μthick.                                                                          thick.                                       ferably 1-6μ thick.                                                      4  A solvent-soluble substan-                                                                      A cross-linked PUE of 0.4-40μ,                                                               *A cross-linked PUE of 0.4-                  tially linear PUE of 0.2-20μ,                                                                preferably 2-12μ thick.                                                                      40μ, preferably 2-12μ                  preferably 1-6μ  thick.        thick.                                    5  A cross-linked PUE of 0.4-40μ, **A cross-linked PUE of 0.6-                 preferably 2-10μ thick.                                                                      None             60μ, preferably                        __________________________________________________________________________                                          3-20μ thick                             *This lamina is softer than the middle lamina                                  **The lamina is softer than the top lamina                               

It is preferred that the Young's Modulus of the top lamina be larger than that of the middle lamina by more than 1 kg/mm², preferably by more than 10 kg/mm², thereby imparting scuff resistance and solvent resistance to the upper layer and giving good touch and enhanced wrinkle properties to the sheet material by being in balanced relation with the flexible lower lamina.

In Case 1, the top lamina comprising the cross-linked polyurethane and the middle lamina comprising substantially linear polyurethane elastomer have high folding endurance. Further the lower lamina increases scuff and solvent resistance of the product and contributes to the bonding of the upper layer to the intermediate layer.

In Case 2, the top lamina, comprising substantially linear polyurethane elastomer, is superior in abrasion resistance and folding endurance and the lower lamina, comprising a cross-linked polyurethane elastomer, is firmly combined with the middle layer giving a product having high durability.

In Case 3, the top lamina comprises a substantially linear polymer and the middle lamina comprises a solvent-soluble substantially linear polyurethane elastomer, so that they are superior in folding durability and the lower lamina increases bonding force between the upper layer and the middle layer.

In Case 4, the composition of the lamina is essentially the same as in Case 2, but in this case the cross-linked PUE is separated into two laminae, that is, the middle lamina which imparts to the upper layer scuff and solvent resistance and the lower lamina which plays a role in binding the upper layer and the middle layer.

In Case 5, the laminae consist of cross-linked PUE alone. In this case the top lamina is rigid and has good scuff and solvent resistance, whereas the lower lamina is supple and has folding resistance.

The cross-linked polyurethane elastomer used for the upper layer may comprise base material, cross-linker and catalyst. The structure of the base material and the ratio of cross linker to the base material are preferably controlled so as to improve scuffing and solvent resistance.

It is preferable, as the substantially linear polymer used for the top lamina in Case 3, to use a polymeric material, films of which have a Young's modulus ranging over 10 kg/mm², such as a substantially linear polyurethane elastomer derived from a polyether or an aliphatic polyester, an organic diisocyanate and a chain extender having a large ratio of diisocyanate to the chain extender, and thus a larger hard segment; a substantially linear polyurethane elastomer derived from a polyester glycol which has an aromatic ring in the molecule, an organic diisocyanate and a chain extender; a polyamino acid resin, a polymethacrylic acid ester, a polyvinyl chloride, a polyester resin, a polycarbonate and cellulose acetate. It is possible to use the polymers listed above individually or blends of the linear polymers with each other and with other polymers.

As the solvent-soluble substantially linear polyurethane elastomer used for the middle lamina of Cases 1 and 3 and the top lamina of Cases 2 and 4, there may be used one obtained by reacting a polyether glycol, such as polyethylene glycol, polypropylene glycol, polyetramethylene glycol, or a polyester glycol, such as polyethylene adipate glycol, polyethylene propylene adipate glycol, polybutylene adipate glycol, polyhexyamethylene adipate glycol and polycaprolactone glycol, or mixtures of these polymers and an organic diisocyanate bifunctional chain extender. It is preferred to use one having high flexibility and high tensile and elongation strength, in order to obtain high abrasion resistance and high folding durability. The polyurethane elastomer may be used alone or in admixture with other polymers mentioned above.

When the bottom lamina and the middle lamina of a 3-laminar upper layer are both cross-linked polyurethane elastomers or where both laminae of a 2-laminae upper layer are cross-linked polyurethane elastomers, it is preferable that the bottom layer be softer than the other layer.

The thickness of the upper layer is critical in obtaining a sheet material having the desired properties. If the upper layer is too thin, abrasion resistance and folding durability of the sheet material are reduced, whereas if it is too thick, the sheet material is heavy and has a hard touch. Accordingly, the optimum thickness of the upper, the middle and lower layers is in the range defined hereinabove.

If thickness of the upper layer exceeds 100 microns, the resultant sheet material is as heavy, hard and cold to the touch as conventional sheet material having a thick polymeric coating, though superior in surface properties. On the other hand, if the thickness is below 1 micron, a sheet material having sufficient surface properties cannot be produced. Preferred thickness is from about 5 to about 30 microns.

As the substrate, use may be made of paper, knitted, woven or non-woven fabric, and their resin-finished products. It is preferred to use a sheet material described in U.S. Pat. No. 3,424,604 issued Jan. 28, 1969, U.S. Pat. application Ser. No. 813,731, filed Apr. 4, 1969 now abandoned and U.S. Pat. No. 3,869,310 issued Mar. 4, 1975.

The sheet material of this invention is able to take such various finishing treatments as surface finishing agents, coloring agents, gloss-finishing agents, applied by spraying or dyeing techniques.

If it is desired to enhance the vapor permeability of the sheet material, the upper layer may be perforated by mechanical means such as needle punching, by means of an electric discharge or by addition and elimination of granules or metal granules soluble in the solvent while the surface coating layer is formed. Each pore should be deep enough to reach through the surface nonporous polymeric coating layer and is approximately 0.1 to 100 microns in diameter, preferably 1 to 50 microns in diameter. The pores are not visible to the naked eye. The number of pores is approximately 10 to 100,000/cm², preferably 100 to 50,000/cm². After the perforating treatment, the surface is subjected to heat and pressure, thus improving surface appearance and properties and further imparting desired patterns. The surface may be heated and pressed by use of a press plate, press rolls or the like, the surfaces of which can be variously patterned according to uses, e.g., smooth surface, aventurine patterned surface, leather-like surface such as calf, kip, kid, buff, crocodile and lizard leather-like patterns and geometrical patterned surface. The sheet material is put to the finishing by ordinary methods of dyeing and spraying coloring agents thus improving its appearance. This invention enables the production of sheet materials of high quality superior substitutes for leathers.

This invention will be better understood with reference to the embodiments described hereinbelow. In the following examples percentages and parts are by weight unless otherwise specified.

EXAMPLE A

A black porous polymeric layer is obtained by providing a polymeric film which consists of a mixture of 8 g/m² of polyurethane elastomer (PUE) and 0.2 g/m² of cellulose octadecylurethane on a polyethylene sheet (support), coating on the polymeric film a solution consisting of 14% of the PUE described above, 2.2% stearyl alcohol, 4% water and 79.8% dimethyl formamide (DMF), coagulating the coating in a coagulating bath comprising 30% DMF and 70% water maintained at 30° C, and then removing the polyethylene sheet and washing and drying it. The polyurethane elastomer is obtained by reacting a polycaprolactone glycol having a molecular weight of 2,000, 4,4'-diphenyl methane diisocyanate (MDI) and ethylene glycol, 5% of water, 1% of carbon black, 2% of stearyl alcohol and 79% of dimethylformamide (DMF).

A fibrous substrate is obtained by making a nonwoven fibrous mat with mixed-spun fibers consisting of 50% nylon-6 and 50% polystyrene, impregnating the fibrous mat with a solution of PUE in DMF which solution consists of 30% PUE (which is a reaction product of polyethylene propylene adipate glycol, MDI and ethylene glycol, 2% sorbitan monostearate, 2.5% stearyl alcohol and 65.5% DMF), coagulating the impregnant in a coagulating bath consisting of 40% DMF and 60% water maintained at 40° C, washing and drying the resultant product and extracting and removing the polystyrene in the fiber by treatment with toluene at 70° C.

The fibrous substrate is bonded on both sides of the polymeric film. The two substrates are then pulled in opposite directions to tear the porous film lengthwise into two halves. In this way there are obtained two sheet materials coated with porous napped film which film has a thickness of 0.25 mm. After painting light brown, this sheet material is pressed with a heated roll in the presence of two parts polyurethane, and in this way it is converted into a smooth porous polymeric layer.

A polyethylene sheet is coated with a solution in DMF of polyurethane elastomer derived from polyethylene glycol, MDI and ethylene glycol to a 6μ thickness of the elastomer, and dried. A roll consisting of polyethylene is coated with a solution of two parts polyurethane in ethyl acetate and a solution of catalyzer in ethyl acetate to a 16μ thickness of the solid component. After removing the major portion of ethyl acetate by evaporation, this coating is transferred to the above described smooth porous polymeric layer. Onto the transferred layer, the polyurethane elastomer layer coated on the polyethylene sheet is placed. Pressure is applied to bond the layers, and after allowing them to stand overnight, the polyethylene sheet is removed.

In this way is obtained a sheet material, on whose smooth surface with naps laid down is bonded a non-porous polyurethane layer having two laminae, the bottom lamina being a cross-linked polyurethane elastomer. After painting light brown and embossing, there is produced a lustrous smooth sheet material with excellent abrasion resistance and blending resistance.

EXAMPLE B

The fibrous substrate is obtained by impreganating a nonwoven fibrous mat consisting of 70% of nylon-6 fibers and 30% rayon fibers with a 25% solution in DMF of PUE (which is a reaction product of polybutylene adipate glycol having a molecular weight of 2,000, MDI and butylene glycol), coagulating the impregnant and washing and drying the coagulated product.

Said fibrous substrate is coated with a solution in DMF of PUE, which solution consists of 13% PUE described in the first paragraph of Example A, 1% polyvinyl chloride, 1% iron oxide, 0.1% carbon black, 5% water, 1.5% stearyl alcohol and 78.4% DMF. The coated substrate is then immersed in a coagulating bath consisting of 30% DMF and 70% water kept at 30° C to coagulate the solution into a porous structure, and washed and dried. The resulting sheet material is napped by abrading the surface of the coated polyurethane layer. The resultant napped porous polymeric layer has a thickness of 0.36mm and a density of 0.20 g/cc.

A non-porous polymeric layer consisting of the same PUE described above which has a thickness of 8μ and a Young's modulus of 6Kg/mm² is bonded to the surface of the napped porous polymeric layer using 8 g/m² of cross linking PUE as adhesive.

Polyethylene film (support) is coated with a mixture of a solution of two-parts type polyurethane elastomer in ethyl acetate and solution of catalyzer in ethyl acetate so as to obtain a non-porous film having a thickness of 5 μ and a Young's modulus of 15Kg/mm², and then the major part of the ethyl acetate is removed by evaporation through a heated zone so that the film retains only slight liquidity and adhesiveness. The film is pressed on the surface of the non-porous polymeric layer and left at room temperature for 40 hours, allowing the solvent to evaporate completely and the film to cure. Then the polyethylene film is removed and the surface of the resulting sheet material is painted brown and embossed.

As a result, there is produced a sheet material having excellent abrasion resistance and good bending resistance.

COMPARATIVE EXAMPLE 1

A solution of polyurethane elastomer (PUE) in dimethyl formamide (DMF), which solution consists of 13% of PUE which is obtained by reacting a polycaprolactone glycol having a molecular weight of 2,000, 4,4'-diphenyl methane diisocyanate (MDI) and ethylene glycol, 5% of water, 1% of carbon black, 2% of stearyl alcohol and 79% of DMF, is spread over a polyethylene sheet (support) to a thickness of 0.6 mm, and is coagulated in a coagulating bath containing 30% of DMF and 70% of water at 30° C. After removing the support and washing and drying the coagulated layer, a porous film of PUE is obtained.

On both sides of the film is bonded a fibrous sustrate which is obtained by impregnating a non-woven fibrous mat consisting of 70% of nylon-6 fibers and 30% rayon fibers with a 25% solution in DMF of PUE which is a reaction product of polybutylene adipate glycol having a molecular weight of 2,000, MDI and butylene glycol, coagulating the impregnant and washing and drying the coagulated product. The two substrates are respectively pulled in opposite directions to tear the porous film lengthwise into two halves and in this way are obtained two sheet materials coated with porous napped film which film has a thickness of 0.25 mm.

The porous polymeric nap on the surface of this sheet material is coated with a solution of two parts polyurethane adhesive in ethyl acetate which solution contains a 10% of the solid component and a catalyzer by means of a coating roll. The roll coating is repeated 3 times with a 140-mesh gravure roll, and the amount of the solid component on the surface becomes 10 g/m². After allowing it to stand at room temperature for 30 minutes, during which time the solvent is almost evaporated, the sheet is pressed with a heated roll having a surface temperature of 155° C, and the naps are flattened. The thickness of the sheet is reduced from 0.25 mm to 0.15 mm and the density of the sheet becomes 0.22 g/cc. There are voids of 50 to 220 μ intermingled among those of several microns on the sheet. Despite the porosity of the surface, it is nearly smooth.

A polyethylene film is coated, to a 20 μ thickness of the solid component, with a mixture of an ethyl acetate solution of two parts polyurethane adhesive (solid content 10%) and an ethyl acetate solution of catalyzer. After removing a greater portion of ethyl acetate by evaporation through a heated zone, the film, which has still some fluidity and adhesiveness, is pressed on the above-described sheet material, and the whole is allowed to stand at 80° C for 30 minutes, thus allowing the solvent to evaporate completely and the cure to proceed.

After removing the polyethylene film, a sheet material is obtained, the surface of which having the laid-down porous polymeric naps, is coated with a nonporous, cured, polymeric film of 16 μ average thickness. On painting it black and embossing it, there is obtained a sheet material having good abrasion resistance, but poor bending resistance.

COMPARATIVE EXAMPLE 2

A polyethylene sheet is coated with a solution in DMF-THF (tetrahydrofuran) (2:8) mixed solvent of same polyurethane elastomer as described in the first paragraph of Example A so as to obtain a non-porous film having a thickness of 22 μ of solid component. After removing a greater portion of the solvent by evaporating through a heated zone, the coated film, which has still some adhesiveness, is pressed on the smooth porous polymeric layer of the same sheet material as described in Example A. After drying it at 80° C, the polyethylene sheet is removed.

COMPARATIVE EXAMPLE 3

A mixture of 50% solution of two-parts polyurethane elastomer in DMF, containing 50% catalyzer and 35% cellulose acetate, is spread on the surface of a polyethylene sheet to make a polymeric film with a thickness of 12 μ, and a Young's modulus of 15 kg/mm². Then ethyl acetate is removed by evaporation. This surface is further coated with a solution, consisting of 15% linear polyurethane elastomer described in the first paragraph of Example A, 15% dimethylformamide and 70% tetrahydrofuran so that the amount of polyurethane elastomer is 5 g/m² to make a polymeric layer of which the Young's modulus is 6 kg/mm². When the solvent has almost been removed by evaporation with 80° C heated air, the same sheet material described in Example A is pressed on it so as to adhere the two layers and then the polyethylene, sheet is taken off.

COMPARATIVE EXAMPLE 4

A polyethylene sheet is coated with a solution in DMF-THF mixed solvent of same linear polyurethane elastomer as described in the first paragraph of Example A so as to obtain a non-porous film having a thickness of 16 μ of solid component. After removing the major portion of the solvent by evaporating through a heated zone, the coated film, which has still some adhesiveness, is pressed on the smooth porous polymeric layer of the same sheet material as described in Example A. After drying at 80° C, the polyethylene sheet is removed.

Then, a polyethylene sheet is coated with a solution in DMF of polyester type polyurethane elastomer having a larger Young's modulus of 4.5 Kg/mm² than the above-mentioned polyurethane elastomer to a thickness of 6 μ of solid component. After removing the major portion of the solvent by evaporating through a heat zone, the coated film which has still some adhesiveness, is pressed on the above obtained linear polyurethane elastomer coated sheet material. After drying at 80° C, the polyethylene sheet is removed.

COMPARATIVE DATA

The sheet materials of Examples A and B and Comparative Examples 1-4 were compared as to their abrasion resistance and bending resistance properties and as to their resistance to deterioration by the action of certain common organic solvents. The data obtained are shown in Table II, which also contains estimates of the sheet materials for the possible use in shoes. The data show that as to the upper layer structure, (1) it must comprise at least two laminae, and (2) the bottom lamina must be a cross-linked polyurethane elastomer.

                                      TABLE II                                     __________________________________________________________________________                              Abrasion                                                                       Resistance                                                                               Bending  Resistance                                                  (Taper Abrasion)                                                                         Resistance                                                                              to solvents                                                                             Estimate                                           weight: 2 lb.                                                                            FLEXO-O-METER                                                                           (alcohol, ketone                                                                        as shoes                         Upper Layer Structure                                                                            mg/1000 times                                                                            (× 1000)                                                                          petroleum)                                                                              Material                  __________________________________________________________________________     Example A                                                                             Top lamina                                                                     linear PUE                                                                     Bottom lamina     45 good   1000                                               cross-linked PUE            very good                                                                               good     very good                 Example B                                                                             Top lamina: cross-linked PUE                                                   Middle lamina: linear PUE                                                                        40 good   750      good     good                             Bottom lamina: cross-linked PUE                                                                            good                                        Comparative                                                                           non-laminar                                                                    (monolayer of cross-linked                                                                       50 good   2.5                                         Example 1                                                                             PUE)                        very poor                                                                               good     poor                      Comparative                                                                           Non-laminar                                                                    (monolayer of linear PUE)                                                                        200 poor  100 poor bad      bad                       Example 2                                                                      Comparative                                                                           Top lamina: cross-linked PUE                                                                     90        500                                         Example 3                                                                             Bottom lamina: linear PUE                                                                        Fair      Fair     Fair     Fair                      Comparative                                                                           Top lamina: linear PUE                                                  Example 4                                                                             Bottom lamina: linear PUE                                                                        190 poor  120 poor poor     poor                      __________________________________________________________________________

EXAMPLE C

Example A was repeated using a substrate which is obtained by the steps described below.

Mixed-spun fibers having 3 deniers and composed of 50 parts of nylon-6 and 50 parts of polypropylene were crimped and cut and the staple fibers obtained were formed into a web by using an air flow. The web was subjected to a needle punching to obtain a three dimensionally entangled non-woven fibrous mat of 600 g/m². The mat was impregnated with a solution consisting of 40 parts of zinc chloride and 60 parts of methanol, which is a non-solvent for polypropylene but is a solvent for nylon-6, at room temperature and the mat thus impregnated was squeezed by a press roll so as to adjust the amount of solution impregnated at 200 g/m². The mat thus treated was left to stand for 20 minutes to allow the major part of nylon-6 in the mixed-spun fibers to dissolve out and to make a fibrous mat consisting of fibers which were composed of bundle of ultra-fine fibers of polypropylene and being impregnated with a solution of the nylon-6. Thereafter, the mat was dipped in water at 50° C for 20 minutes to coagulate and deposit the nylon-6 solution between the fibers uniformly in cellular polymeric structure and then treated with water at 80° C to remove zinc chloride and methanol and dried.

EXAMPLE D

The substrate in Example A was coated with a polyurethane adhesive, and porous polymeric particles were then bonded thereto. The polymeric particles were obtained by coagulating a solution in DMF containing 75% PUE derived from polybutylene glycol, MDI and butylene glycol and 15% polymethyl methacrylate and 10% brown pigment as solid component into a porous structure and pulverizing the porous structure. Thus, a finely napped porous polymeric layer bonded on a substrate was obtained.

On the finely napped porous polymeric layer, a layer of cross-linked PUE, which had been made on a metallic roll covered with polyethylene, having a Young's modulus of 0.5 Kg/mm² and a thickness of 10μ, was transferred. Next, on the layer of cross-linked PUE, another layer of cross-linked PUE, which had also been made on a metallic roll covered with polyethylene, having a Young's modulus of 2 Kg/mm² and a thickness of 6μ, was transferred. On said layers, a top layer of PUE derived from polyethylene glycol, which had been made on a metallic roll, containing 10% brown pigment and having a Young's modulus of 25 Kg/mm² and a thickness of 3μ, was transferred. The resulting sheet material was then embossed.

EXAMPLE E

A polyethylene sheet is coated, in a film thickness of 8μ, with a solution in DMF of polyurethane elastomer described in Example A (Young's modulus = 8.5 Kg/mm²), and after desiccation, this is bonded with two-parts type polyurethane on the substrate in Example A and left to stand for 40 hours. Then the polyethylene sheet is removed. The layer of polyurethane is covered with a 3μ thick film of PUE described in Example A with a high Young's modulus (20 Kg/mm²) by coating with a solution in a mixture of DMF and tetrahydrofuran by means of gravure roll. The surface is then embossed and painted black.

The sheet material thus obtained has strong resistance to bending and fatigue and is good in appearance. It is suitable for use in upholstery, covers, handbags, shoes, etc. 

What is claimed is:
 1. A sheet material having leather-like grain, excellent scuffing and abrasion resistance and superior dyeability comprising in combination a fibrous substrate, an intermediate layer consisting of a finely napped porous polymeric layer bonded to said substrate and an upper layer consisting of a non-porous laminar polymeric layer completely covering and bonded to said finely napped porous polymeric layer,said finely napped porous polymeric layer having a thickness of about 0.05 to 2.5 mm., a density of about 0.25 to 0.5 g/cc, a nap length of about 0.03 to 0.5 mm., and minute pores of about 0.1 to 100 microns in diameter, and said non-porous polymeric layer having a thickness of 1-100 microns and consisting of a laminar structure of at least two polymeric laminae exhibiting different physical properties, of which the lamina thereof bonded to said finely napped porous polymeric layer consists of a cross-linked polyurethane elastomer.
 2. The sheet material of claim 1 wherein the other laminae of the upper layer are derived from cross-linked and/or solvent-soluble substantially linear polyurethane elastomer.
 3. The sheet material of claim 1 in which the upper layer has 3 laminae wherein the top lamina is a polyurethane elastomer having a Young's modulus at least 10 kg/mm² greater than that of the middle lamina.
 4. The sheet material of claim 2 in which the upper layer has 3 laminae, wherein the top lamina consists of a cross-linked polyurethane elastomer and the middle lamina consists of a solvent-soluble substantially linear polyurethane elastomer.
 5. The sheet material of claim 2 in which the upper layer has 2 laminae wherein the top lamina consists of a solvent-soluble substantially linear polyurethane elastomer.
 6. The sheet material of claim 1 wherein the intermediate layer is formed of a polyester, a polyamide, a vinyl polymer, or an elastomeric polymer.
 7. The sheet material of claim 6 wherein the intermediate layer is formed of a polyurethane elastomer.
 8. The sheet material of claim 2 in which the non-porous polymeric layer has a thickness of 5 to 30 microns.
 9. The sheet material of claim 1 wherein the upper non-porous polymeric layer is perforated to form pores not visible to the naked eye which extend through said non-porous polymeric layer and at a density between 10 and 100,000 pores/cm².
 10. The sheet material of claim 2 wherein the upper non-porous polymeric layer is perforated to form pores not visible to the naked eye which extend through said non-porous polymeric layer and at a density between 10 and 100,000 pores/cm². 